Патент USA US2269485код для вставки
3m. E3, E942. V.V A. SÀLMI 2,269,485 PROCESS l'ï‘OR THE CONVERSION OF ASPHALTIC HYDROCARBONS Filed Jan. 9, 1940 F04 THR FIRM ,4free/vars. Patent-ed Jan. lf3, UNITED STATES ~lui'rlazrn‘ oFFicEf PROCESS FOR THE CONVERSION Y0F l ASP-BALTIC HYDROCARBONS . Y vaines. salmi, Culver city, cam., [email protected] ,to Metallytic Corporation, Los Angeles,` Calif., a, Application corporation Januar-ys, ofCalifornia 1940, - sei-alim. " _ 313,034 ` ' » >`¿ 1o claims.. gorras-1o) v ‘y ` ’_ l l' VAl simple, economical process-fori vthe -complet This invention relates tothe conversion,"of> »sphalt or asphalt-like hydrocarbons into hydrir'Ã`l` ' conversion -of asphaltic bodies’ lntoâollsg-offî'thef :arbon oils falling within the boiling point range ' "lubricating oil boiling point range,j-'byf.a.'g-~simple »t lubricating oils; this conversion being accom , heat treatment 'without the‘use of :hydrogenëarid-V nlished by a simple heat treatment, without the »dditionof hydrogen'or use of chemicals.` 'I'hese without.y any appreciable loss or'vi'ormation` of fany. undesirable- by-products, would.t.herefore-'be„v`al lsphaltic hydrocarbons occurv in nature either uable, not only froml 'the‘vievvpointfofflubricating.i is -such or together with lighter hydrocarbons ’ , -' values, b_ut also from the'vieWpOintof»'overcom-' n petroleum, also in the'destructive distillation ' _ingrefining diñiculties and reducing theare'finingl »roducts of coal, shale, peat, wood, etc. In such 10 losses and from'the viewpoint oflproducingysuwï »roducts and especially in petroleum, asphaltlc ' »odies form the least valuable constituent- and Derior fuel oils'andmore desirable`- tocks'for. i cracking operations; n the refining of such products for variousl in Y I it is an objectA of my inventionrto :rovideca: lustrial uses', the asphalt presents one ‘of the method of - simple and'eilicient. character ,wherea ,Teatest problems not only from a purely techni-A 15 "by vheavy hydrocarbons may >'be Íconverted pinto;y 1al, but also from a commercial viewpoint. lighter hydrocarbons and-'whereby-a‘substantial l Thus, in the separation of the various constit conversión yof ‘asphalt or asphalt-like'íresidues *_ j lents of petroleum by distillation, not only are he asphaltic bodies separated with diillculty ' into treatment, hon conversion lubricating. and in method >ofilqn‘iay generalbe for toobtained-by the'manufacturexotr4 provide la-»hydrocarv pyrolytic '~ f . rom the most valuable fractions; that is, the ieavy lubricating oils, but the tendency is for lubricating stocks of superior oils, fuel quality. oils, or overhead . « '_ cracking ' he lubricating Voil fractions to revert >into lsphalt. Moreover, the asphaltic residues may If have discovered that if asphaltic- hydrocar->e disposed of only as low grade fuel oils or as ' he least desirable raw stock for cracking proc sses. bons are brought into contact with rni'iltenîsub-- -f stances or at any ratek with molten metals-orf .alloys for a certain, short period of time, ata" ' ` In the cracking of the asphaltic- oils witha .certain temperature.. they are ‘converted ‘into "lew of producing lighter motor fuels, formation, lubricating oils and I_,have discovered means of. »f coke and noncondensabie gases soon sets in, producing-and maintaining the necessary condi :as oil or lubricating oils are used as starting ma tical 1 esnlting in a yield of gasoline lower than what 30 _tions as regards the tirneelement,temperature.;-` " V would be theoretically expected, taking into con heat transfer, and contact, so that the reaction lderation the hydrogen content of the original can be maintained indefinitely or at least to suchV an extent that such asprocess becomes of prac tock. When overhead stocks such as kerosene, value. - ~ ‘ l ` ` l » . ' The conversion _of asphaltic hydrocarbons. by this process into lighter oils falling'malnly with-' erial, a much more satisfactory decomposition eaction ñrst takes place, but eventually asphalt ormation sets in, resulting lultimately in th'e for nation of coke and non_condensable gases, where in the boiling point range of oils classed as lubri‘-, eating oils, may be made highly efñcient; that is. l - Iy valuable hydrogen is’lost. side reactions producing undesirable by-products ' -« ' ~ -~ l, In milder cracking operations, where effort is 40 ysuchaskflxed gases, coke- or other valueless or detrimental products may .be largely suppressed 1;@ cade to convert residualv oils into fuel oil of uwer viscosity, into oil stock more suitable for to give a substantially complete yield of lighter '~ ntensive cracking operations, or even into lubri oils on the basis of the asphalt converted. How- ‘ ating oil, the processes now known are capable 45 " ever, as the _time element is veryshortfit ls dim f only partial conversion of asphalt, if the actu cult _to establish and maintain conditionsab‘so' l asphalt content of the stock is taken into con lutely ideal as__regards every particle Iof'asphait> ' lderatlon. Moreover, if recovery of lubricating passing being that througlì'the'reaction¿zonépthegresult" part of the asphalticfsubstance re-„ml ' ils or other valuable oil fractions is attempted as separate distillate, a large part of the stock 60 mains unconver-ted in a singlepassaggfthrough the process. This unconverted asph'azlt'fV~ not, forked upon will remain as residue of less value han the original stock and unilt for further however, differ substantially from"the"'original nnversion by the same process, except under onditions where coke and gas formation takes material and may in most instances be by the same process, as by simply> returning it lace. ‘ 55 into the process with `fresh feed stock, or by treat., 2 matassa ing it separately. if necessary at a higher tem short, is partly dependent on the exact nature perature. of the asphaltic oil stock worked upon. on the temperature of the contact medium, on the tem As stated, the necessary time element is very perature of the incoming oil, etc. However, the short. This is controlled in part at least by keeping the amount of hydrocarbon material in 5 procedure necessary in each case will be made clear from the disclosures given further on. In the reaction zone to a minimum relative to the available contact surface.v If the unconverted. general, `the contact period should be sumciently portion of the «asphalt is not removed almost immediately, or within a certain time limit, de pending on the temperature employed, it will polymerize and eventually decompose with the formation of carbon or coke, which carbonor " short to insure that the hydrocarbon material. typically unconverted asphalt, is not substan tially decomposed into coke, nxed gas etc., auch decomposition being prevented by removing the coke will rapidly foul the contact medium or metal bath, in many cases within a few minutes, to such an extent that the converesion reaction asphalt before it reaches excessive temperatures or before substantial decomposition sets in due to protracted contact at elevated temperatures; orboth. of asphalt into lubricating oil will be completely arrested. despite the fact that the time element and temperature might be suitable for converf accomplished, first by introducing the asphalt or oil containing it either upon the surface of the The proper, short time element for contact is metal bath or a- short distance below it, such as sion. Whether the molten substance, such ss molten 20 a few inches. and second by rapid or immediate lremoval of the converted products from contact with the bata by rapid or immediate veintiun tion. induced by maintaining a sufilciently high temperature in the molten bath and employing metal or alloy. _called here’the contact medium. acts in the process disclosed here in the _role of s catalyst, isïnotcertain. 'As arule, the `reactions produced by catalysis are >specific 'to certain sub stances. whereas to my knowledge the conversion reaction here can be brought about by.. 'any known means capable of( increasing the volatility of the oils produced. such as 4vacuum and/or carrier gases, but especially steam, inert contact Íwith -any molten. substance. ,as far as a substance is used lthat does not en--` v, gases, and the like, which I have found most effective and economical. The use of steam or other eifective means of and thus` make >it dimcult to determine the cause 50 of the reactions produced. At any rate, I have Y ‘ increasing volatility, is especially important from ter into chemical Areaction with the asphaltv successfully used tin, lead, and zinc, both singly and in combination, one with another, and in combination withantimony. , i ` On the; other hand, therapidity 4with which heat is;` transferable from the molten metal to , the small globules or iilms of asphalt material4 may be an important factor in the process. The depolymerization or conversion reaction by which asphaltis converted into lubricating oil may be initiated at elevated temperatures, but is appar ently endothermic in character, and a continued _ and rapid input'of heat is required to maintain this reaction 1in ascendancy over undesirableA side-reactions leading to degraded products, coke the viewpoint of immediately removing any un- i converted asphalt from contact with the bath. if ' temperaturesappreciatly above 400° C. are main tained in the bath.V »If -temperatures below 400'` C. are maintained in the bath; it is however pos sible toallow theasphalt to remain in contact ç with the bath a somewhat longer period, so that it may be allowed to float on top of the bath and is drained of! as rapidly as' possible. The steam may be introduced into the molten bath at any level, preferably at a lower ie'vei than the asphal tic rawI stock. The steam does not decompose or enter into reaction with the oil; the water re» _' covered‘in the condensate is equal to the water etc, Attempts to obtainthis rapid heat transfer .. fed in as steam. through poorly conducting surfaces. e. g.. solid surfaces; wouldrequire such a high temperature 'I‘he feed stock need not be preheated when temperatures appreciably over 400’ C. are main . surface ydeposition, of coke, thus defeating further tained in the bath, but with lower temperatures. preheating of the stock becomesV advisable; in conversion. By the use of molten metal, however, which case a preheat temperature of 'about 250° y conversionsl at _a hydrocarbon temperature oi ' C. version. is sumcient Due to to the insure short a high contact degree period of con-` the -, ._ ' differential as to resultin local over-heating and 27_5’ to 375° C. may be maintained with a tem temperature of the oil or oil vapors is' not brought ` peraturemmerential such for example that the metal temperature need be only 450’ to 550’ C. ~ up to the temperature of the contact medium or bath, in fact a contact period should be estab The rapidity -Qf heat transfer is further aided by the agitationxor circulation of the «molten metal. ' lished of only sumcient duration to heat the stock l to a point where the convertedhproducts. and in case- of higher temperatures in the bath also ï the unconverted asphalt, are volatilized with the aid ofsteam. Thetemperature of the vapors for the more or less abrupt heatingofthe asphalt to the desired'conversionj temperature;- L e.. t0 ' is usually around 300° C. It is to bestated here that with a high temperature'in thebath, such as, 'c avoid preheatingforfother pretreatment involv- ` for instance 450° C. and over,`a_ny unconverted ing heating of thestcch` to elevated temperatures.> Por example,- asphaltic' crude oils are sometimes 65 asphalt is readily volatillzed together with the converted products, provided suilicient steam or more amenable to conversion than are topped other carrying gases and/or vacuum are used. residual fractions obtained therefrom. In other despite the fact that the temperature of the instances, however, preheating of the conversion vapors may not be over 300° C.- This volatiliza stock immediately prior to conversion induces no noticeable change and is of adi'. antage in reducing 70 tion of asphalt under such conditions may not be due to actual z'aporization, butto mechanical the heat load on> the molten metal. To specify the actual time element necessary carrying over, such as in the form of a fog. I have found that in many instances my inven for the asphalt lubricating cil reaction, that is. tion may be advantageously practiced with the to specify it in ruiaitsoi' time. is difficult, as the contact timenecessary«fory conversion is .very molten metal at a _temperamrepf 450°" to 550’ duction otthefheat is . 1ny were. instances 1t u advantageous 'to provide _. 2,209,485 4 I claim ‘as-'my invention: turning the heavy, asphaltic 'bottoms back into the process with fresh feed stock. a complete conversion of the asphalt present in the crude oil was_aecomplished. >The converted distillate or asphalt-tree, overhead therefrom could~be var iously utilized The lubricating oil fractions were equal or superior to thelubricating oil 'originally associated with the crude, and also constituted an excellent cracking stock‘ for liquid o_r vapor phase cracking, as well as a blending stock for fuel oils.> . V i i . „ ' l . Example No. 2 The; same »crude oil _as-'in Example No. 1 was treated kby passing it through' a molten alloy; con i 1. A method of. converting asphaltic hydrocar bon of the character ydescribed `to lubricating oil, comprising‘the steps of: bringing said as phaltic hydrocarbon into substantially momen tary contact with a body of molten metal main tained at such _a temperature in the range of 450° to 550° C. that said asphaltic hydrocarbon will be brought to a temperature within the range of 2‘75‘ to 375° C.; and dlsengaging the asphaltic hydrocarbon and resulting converted products brought to said temperature. from further con tact with` the molten metal by-volatilization and atomizaticn in a concurrent now of both volatil ized' and nonvolatilized portions with `steam so adjusted. that substantially no converted or un -converted asphaltic hydrocarbon is left in con tact with the molten metal for periods exceeding the desired momentary contact. sufiic'ientlyìî‘fiuidfatî‘all~î tunes;f . The. oil was' -pre 2. A method of converting asphaltic hydrocar heated »tizsoë-chiiu introduced inte ,the .molten , >alloy tinches‘beiow the surface; The alloyrwaa ’ vbon ofthe character described t0 4lubricating oil comprising the steps of: bringing said asphaltic .kept -at a' temperature >of-3'10‘ C. and steam hydrocarbon into substantially momentary con .nmountign'i‘to -40% lof thejcrude 'was introduced ‘ through» another >-f’eed line; also 4' inches below ' tact with a body of molten metal maintained at tlie___surface.‘f~Infthis case, due to the low tem‘ 25 such temperature that said asphaltic hydrocarbon will be brought to a temperature within its tem perature maintained in‘the alloy, the portion of perature range of conversion as the result of asphalt remainingv unconverted was’not volatil Y ized 'orfcarried-over by the vapors. but remained said contact with molten metal, whereby a sub stantially complete conversion of asphaltic sub on topbfíthe'alloy 'and »wascontinuously drained sisting-o'l 80%.» of ~leadìandlofit of antimony, this alloy having a' meltingpoint sufficiently far below Vthe temperature ‘employed in'thlß‘ oase to keep it out as'rapidly’asïpossible. «1 With-such a low‘tem- , 30 -stanceíto lubricating oil isV obtained without sub -perature .inthe alloy. theasph’alt will ?otooke ‘ine stantial formation of coke, gas, or other reversion products; and disengaging the asphaltic hydro the-time required Vfor draining despite the. fact carbon and resulting converted products'brought that under such- conditionsit remains incontaot with the bath a longer period thanincaseswhere ` to said temperature from further contact with the the asphalt is removed by volatilization. The as 35 molten'metal by volatilization and atomization _phalt or lresidue..drained on the surface of the ,_ in a concurrent flow of bothvolatilised and non volatilized portions with steam so adjusted _that . alloy amounted to 15% Aof theie‘rude oil treated. The combined distillate` was'free .from asphalt. 'Bhe asphalt content was therefore reduced from '11% m1569721;` . -No coke >or gas formation took place and the totalfyield of voil and asphaltic residue was 100%. It was found that the remaining asphalt drained ofi the> surface yof the bath could not be converted by ’returning itback into the process with freshfee'd stock.;- However. »conver sion of~ this residue was-accomplished-by employ ' lng a procedure. similar to theone given under Example No.--1~and maintaining in the. bath a temperature `of :about 550°' C. . " “rxàmpleivd 3 An. Oklahoma 4crtule petroleum was used in this substantially no converted Vor unconverted as phaltic hydrocarbon is left in'contact with the 40 molten metalfor periods in excess of the desired momentary contact. ‘ 3. A process for converting asphaltic stock of the character described into lubricating oil, com prisingz' maintaining a body of molten metal in a reaction zone at a temperature from about 375’ to about 550° C.; agitating said metal by `intro ducing therein a stream of carrier gas and per mitting said gasto escape from the upper surface n of the metal; continuously bringing the asphaltic w. stock into said reaction zone to contact the molten metal at a level not lower than a few inches below the upper surface of the metal; adjusting the - stream of carrier gas to volatilize lubricating oil case. l'I‘hisfcrude is extensively used for the fractions present in the stock and formed by con manufacture oflubricating oils, but contains 55 v version thereof to produce an' eiiiuent stream of about 5% of asphalt and when distilled in the gas andrhydrocarbon vapor having a temperature ordinary. manner vproduces lubricating oil stocks not greatly in excess of 300° C.; and continuously which require .acid refining, with consequent removing any non-‘volatile asphalt from the upper heavy.losses,.-.«before they'can bennisbed to a surface of the metal to prevent protracted con- ' proper c_olor with absorptive clays. tact thereof with the molten metal. distilledin a manner similar to theonegivenun der Example No. '1, except that’sthe temperature of theV lead bath was maintaineftlvat 4251"- C. and the amount of steam usedïwfailáiil7a.> The yield of oil recovered was.' approximately' „100% and no carbon or coke formationfítooiì ace. The lubri cating oil stock producedlwasthen_treated with absorptive clays withoutjl “preliminary acid re :ming 'and an ou witnîsîs ’haard _com was ob 60 4. A process as in claim_3 in which the' ‘asphaltic « stock is introduced into the reaction zone at a level not lower than four inches below the surface of the molten metal. ' ' ' ‘ ’ i 5. A process for converting asphaltic stock of 65 lthe character described into lubricating oil, com prising: maintaining a body of molten metal at a temperature from about 375° to about 450° C.; introducing the asphaltic stock into said metal at tained, while the Alubriciaitn'ig 'oil' stock obtained a depth of not over a few inches from the upper from the same crude ’byßordi'?ary distillation 70 surface thereof; introducing a stream of carrier methods could not be treated and finished with gas into the body of molten metal to cause agi absorptive clays without preliminary acid refining. tation thereof and to aid in the volatilization oi This application is a continuation-impart of the lubricating oil; adjusting the relative rates of my copending applications, Serial Nos. 142,560 76 introduction of asphaltic stock and carrier gas and 166,307. 5 - 2,269,485 into the molten metal to cause complete and con tinuous volatilization at temperatures not greatly in excess of 300° C. of lubricating oil fractions 8. A method as in claim 'I in> which the stream of carrier gas is adjusted to scavenge the surface of the molten metal and maintain it substan produced by conversion of the asphalt in the tially clean, whereby the quantity of hydrocar presence of the molten metal; and continuously withdrawing non-volatile fractions accumulating 5 bon material in contact with the molten metal at a given instant is minimized. on the upper surface ofthe molten metal. 6. A process for converting asphaltic hydro carbons into lubricating oil, comprising the steps 9. A method of converting asphaltic hydro carbons of the character described into lubricat ing oils, comprising: continuously bringing the of: maintaining a body of molten metal in a re action zone at a temperature from about 450° to l0 asphalticA hydrocarbons into contact with the sur about 550° C.; passing a current of steam there through; introducing the asphaltic hydrocarbon into said reaction zone‘ at a level not lower than a few inches below the surface of the molten metal face of a body of molten metal; maintaining the temperature of the metal above 450° C,; and re moving'the converted and any unconverted hy drocarbons from_ contact with the metal by to contact the metal and induce at least partial l5` volatilization and atomization in a concurrent conversion thereof into lubricating oil; and ad ì i'low with a stream of a carrier gas so adjusted that the temperature of the ellluent stream of v vapor and gas does not substantially exceed phalt and conversion products from the molten » 300° C. metal in a concurrent stream of vapors and atom- ` 20 justing the current of steam to remove the as ized particles. l 7. A method of converting asphaltic hydro carbons into lubricating oils, which comprises the steps of: continuously bringing said asphaltic 1.0. A method of converting asphaltic hydro carbons of the character described into lubricat ing oil. which comprises: bringing the asphaltic hydrocarbons continuously into contact with the surface of a body of molten metal maintaining hydrocarbons into contact with the surface of a body of molten metal; maintaining the tempera 25 the temperature of the metal in a range from ture ofthe metal in the range from about 450 to' 550° C.; and continuously disengaging the result ing converted.` product and any unconverted hy drocarbon >from contact with the molten metal by volatilization4 and atomization in a concurrent 30 now of both volatilized and unvolatilized por-‘ tions with a stream of a carrier gas, so adjusted that substantially no converted or unconverted hydrccarbons are left in contact with the molten 35 metal beyond a momentary period. about 350° C. to 450° C.; agitating said metal with a current of carrier gas adjusted to produce an emuent stream comprising gas and hydrocarbon vapor, the temperature of said stream being not greatly in excess of 300° C.; and continuously re moving any non volatile asphalt from the upper surface of the metal to prevent protracted con tact thereof with the molten metal. VAINO A. BALMI.